2-substituted phenylhydrazonoimidazolenine fungicidal and bactericidal agents

ABSTRACT

2-SUBSTITUTED PHENYLHYDRAZONOIMIDAZOLENINE FUNGICIDAL, BACTERICIDAL, INSECTICIDAL AND ACARICIDAL AGENTS OF THE FORMULA   IN WHICH R is alkyl of up to 16 carbon atoms, R&#39;&#39; is hydrogen, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, alkylsulfonyl or optionally substituted arylsulfonyl, X is halogen, alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, dialkylamino or nitro, and M IS 0 TO 4, WHICH COMPOSITIONS EXHIBIT EXCELLENT FUNGICIDAL AND BACTERICIDAL PROPERTIES AS WELL AS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent [191 Buchel et al.

[ Z-SUBSTITUTED PHENYLHYDRAZONOIMIDAZOLENINE FUNGICIDAL AND BACTERICIDAL AGENTS [75] Inventors: Karl Heinz Buchel,

Wuppertal-Elberfeld; Paul-Ernst Frohberger; Hans Scheinpflug, both of Leverkusen; Edgar Enders, Cologne, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 22 Filed: June 12,1972

211 Appl. No: 261,828

[44] -Publishegl under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 261,828.

[30] Foreign Application Priority Data June 15, 1971 Germany 2129524 [52] US. Cl 424/273; 260/309 [51] Int. Cl. A01N 9/22 [58] Field of Search 424/273; 260/309 [56] References Cited OTHER PUBLICATIONS Fargher et al., J. Chem. Soc., (London), Vol. 115, 1919 pp. 217-260.

[451 Dec. 9, 1975 Primary ExaminerAlbert T. Meyers Assistant ExaminerAllen J. Robinson Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT 2-substituted phenylhydrazonoimidazolenine fungicidal, bactericidal, insecticidal and acaricidal agents of the formula Rlls-ng l 9 Claims, No Drawings Z-SUBSTITUTED PHENYLHYDRAZONOIMIDAZOLENINE FUNGICIDAL AND BACTERICIDAL AGENTS The present invention relates to and has for its objects the provision of particular new pesticidal compositions comprising 2-alkyl-4-phenylhydrazonoimidazolenines which may be substituted on the phenyl ring and which may be acylated on a hydrazone nitrogen atom, which compositions possess fungicidal, bactericidal, microbicidal, insecticidal andacaricidal properties. The invention also covers mixtures of such compounds with solid and liquid dispersible car rier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g., fungi, bacteria, microbes, insects and acarids, especially fungi and bacteria, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that zinc ethylene-l,2-bis-dithiocarbamate is effective as a protective leaf fungicide. It is used for the control of potato blight, of brown rot of tomatoes, of fruit scab, banana leaf spot and mildew diseases. Furthermore, it is in use as a seed dressing and soil-treatment agent. It is disadvantageous that zinc ethylene-1,Z-bis-dithiocarbamate (Compound 4) when applied in small amounts and low concentrations shows only a very slight effect, since it does not become effective until it degrades into volatile substances, such as isocyanates (see R. Wegler, Chemie der Pflanzenschutzund Schadlings-bekampfungsmittel, Volume 2, pages 6-7 (1970); Springer-Verlag, Berlin). Moreover, its effectiveness against fungal diseases of rice is inadequate.

The present invention provides pesticidal compositions comprising the phenylhydrazonoimidazolenines of the formula rams-mg (I) in which R is alkyl of up to 16 carbon atoms,

R is hydrogen, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, alkylsulfonyl and optionally substituted arylsulfonyl,

X is halogen, alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, dialkylamino or nitro, and

m is to 4,

which compositions exhibit excellent fungicidal and bactericidal properties as well as microbicidal, insecticidal and acaricidal properties.

Surprisingly, the I new 2-substituted phenylhydrazonoimidazolenines according to the present invention show a considerably better and broader fungitoxic effectiveness than zinc ethylene-l,2-bis-dithiocarbamate, which is known from the prior art. The compounds according to this invention therefore represent an enrichment of the art.

In the formula (I), it is preferred that R should be straight-chain or branched alkyl with up to 6 carbon atoms, especially lower alkyl such as methyl, ethyl,

m-propyl, m-butyl, isopropyl or tert-butyl; that R should be hydrogen, an alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl radical wherein the alkyl moiety contains from 1 to 6 carbon atoms, lower alkyl such as methyl, ethyl and isopropyl being especially preferred; or an arylcarbonyl, aryloxycarbonyl or arylsulfonyl radical of which the aryl moiety contains 6 to 10 carbon atoms, phenyl being especially preferred, in the case of an arylsulfonyl radical the aryl being optionally,

(the alkyl radicals of the latter being identical or different) with up to 6 carbon atoms in each alkyl radical, or nitro; and that m should be 0 to 3, especially 1 or 2.

Fargher et al. in J. Chem. Soc. (London) Vol. I15 (1919) at page 256 disclose two compounds whose use falls within formula (I), viz:

2-methyl-4-phenylhydrazonoimidoazolenine, and

2-methyl-4-p-bromophenylhydrazonoimidoazolemne, but no utility therefor is recited. Thus, those compounds are new wherein m is l to 4 or wherein R is alkyl of 2 to l6 carbon atoms.

The present invention also provides a process for the preparation of 2-substituted phenylhydrazonoimidazolenine of the formula (I) in which a. an imidazole of the general formula I ll (r1) R N I in which R has the meaning stated above, is reacted with a diazonium salt of the general formula 9 cl (III) in which X, Y, m and n have the meanings stated above, in the presence of an acid-binding agent and optionally in the presence of a diluent, or

b. a phenylhydrazonoimidazolenine salt of the gen-.

eral formula I X R N nun-Q m (1v) I .Na v n in which R, X, Y, m and n have the meanings stated above, is reacted with an acid chloride, chloroformic acid ester or sulfonic acid ester chloride of the general formula 3 9- Cl-C-OR" (V or o N Cl-S-OR" II) in which R" is alkyl or aryl, or in formula (V) optionally subcarbonate. Sodium carbonate is particularly suitable.

The reaction temperatures in process variant (a) can be varied within a fairly wide range. In general, the work is carried out at from about 20 to +20C, preferably from about 5 to +5C.

stituted aryl, optionally in the presence of a diluent. 10 When carrying out process variant (a), there are If 2-isopropylimidazole and phenyldiazonium chloride are used as starting materials in process variant (a), the reaction course can be represented by the used, in general, equimolar amounts of the starting materials. Deviation from the stoichiometric proportion is possible, but brings no substantial improvement following equation: of yield.

l CH -CH N 121; :1 9 W (in H (Ila) (Illa) N III III/KIlII (VIII) H If the sodium salt of 2-isopropyl-4-phenylhydrazonoimidazolenine and chloroformic acid methyl ester are used as starting materials in process variant To isolate the compounds of the formula (I) that are prepared according to process variant (a), it suffices to filter them out of the reaction mixture, since they are (b), the reaction course can be represented by the obtained in crystalline form. They are purified by refollowing equation:

3 (VIa) oo-ocn The imidazoles (II) that are used as starting materials are known.

A number of phenyldiazonium salts (III) to be used as starting materials are known. Those that have not hitherto been described in the literature can be prepared by methods analogous to the methods used to crystallization.

solvents are suitable. Preferred solvents are hydrocarbons, such as petroleum ether, benzene, toluene or xylene; ethers, such as dioxane or tetrahydrofuran; nitriles, such as acetonitrile or benzonitrile; alcohols, such as ethyl alcohol, isopropyl alcohol or butyl alcoprepare the known ones (see Houben-Weyl, Methoden hol; or halogenated hydrocarbons, such as methylene der Organischen Chemie, Volume 10/3, Georg- Thieme-Verlag, Stuttgart, page 514 [1965]), as described in Example 1 hereinbelow.

The phenylhydrazonoimidazolenine salts of the formula (IV) to be used as starting materials have not yet been described in the prior art; as exemplified hereinbelow, they can be prepared by reacting 2-substituted phenylhydrazonoimidazolenines of the formula (I), in

which R is hydrogen, with equivalent amounts of sodium ethylate.

The acid chlorides (V), chloroformic acid esters (VI) and sulfonic acid ester chlorides (VII) to be used as starting materials are known.

When carrying out process variant (a) according to the invention, in general a diluent is used. Especially suitable for this purpose are aqueous solvents or aqueous solvent mixtures. The reaction is, however, preferably carried out in water.

As the acid-binding agent, any usual acid-binder may be used, especially an alkali metal hydroxide, such as chloride or chloroform.

The reaction temperatures in process variant (b) can also be varied within a fairly wide range. In general, the work is carried out at from about -20 to +50C, preferably at from about -5 to +40C.

When carrying out process variant (b) there are used, in general, between 1.1 and 1.5 moles of the compound of the formula (V), (VI) or (VII) per mole of the compound of the formula (IV). Further exceeding of the stoichiometric amount brings no substantial improvement of yield.

'Theactive compounds according to the invention exhibit a strong fungicidal activity. In the concentrations necessary for the control of fungi they do not damage cultivated plants and they have a low toxicity to warm-blooded animals. Forthese reasons, they are suitable for use as crop protection agents for the conof plants or attack the plants from the soil, and seedborne pathogenic fungi.

The active compounds according to the invention have given good results particularly in the control of rice diseases. Thus, they have shown an excellent activity against the fungi Piricularia oryzae and Pellicularia .sasakii, by reason of which they can be used for the 1 joint control of these two diseases. That means a substantial advance, since up to now agents of different chemical constitution have generally been used against these two fungi. Surprisingly, the active compounds show not only a protective activity, but also a curative effect.

The active compounds are likewise highly effective and of particular practical importance when they are used as seed dressings or soil-treatment agents against phytopathogenic fungi that adhere to the seed or occur in the soil and cause, in cultivated plants, seedlings diseases, root rots, tracheomycoses and stem, stalk, leaf, blossom, fruit or seed diseases, such as Tilletia caries, Helminthosporium gramineum, F usarium nivale, Fusarium culmarum, Rhizoctonia solani, Phialaphora cinerescens, Verticillium alboatrum, Fusarium dianthi, Fusarium cubense, Fusarium oxysporum, Fusarium solani, Sclerotinia sclerotiorum, Thielaviopsis basicola and Phytophthora cactorum.

The active compounds according to the invention have, for instance, also proved effective against Cochliobolus miyabeanus, Mycosphaerella musicola, Cercospara personata, Botrytis cinerea and Alternaria species. Phytopathogenic bacteria species, such as Xanthomonas oryzae, can also be controlled.

Furthermore, the active compounds according to the invention are also effective as leaf fungicides; they can for example be used with success againts Erysiphe and Fusicladium species.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g., conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g, conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xy- 5 lene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes, etc.), cycloalkanes (e.g., cyclohexane, etc.), paraffins (e.g., petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g., methylene 10 chloride, chloroethylenes, etc.), alcohols (e.g., methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g., glycol monomethyl ether, etc.), amines (e.g., ethanolamine, etc.), amides (e.g., dimethyl formamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground erals (e.g., highly dispersed silicic acid, silicates, e.g.,

etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other fungicides, bactericides, microbicides, insecticides and acaricides, or

rodenticides, nematocides, herbicides, fertilizers,

growth-regulating agents, etc. if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0. l95 percent by weight, and preferably 05-90 percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 0.01-1 percent, by

weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid,

and/or (2) a dispersible carrier liquid such as aninert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- percent, and preferably 0.01-95 percent, by weight of the mixture.

In the case of seed treatment, there are required, in

natural minerals (e.g., kaolins, clays, alumina, silica,

7 general, amounts of active compound of 0.1 to 10 g, preferably 0.5 to 5 g, per kg of seed. For soil treatment, amounts of active compound of 1 to 500 g, preferably 10 to 200 g, per cubic meter of soil are generally required.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g., average particle diameter of from 50-100 microns, or even less, i.e.,

mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid-compositions with said liquid carrier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the 100 percent active substance alone, e.g., about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g., fungi, bacteria, 'microbes, insects and acarids and more particularly methods of combating at least one of insects, fungi and bacteria, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, such fungi, (d) such bacteria, (e) such microbes, and (f) the corresponding habitat thereof, i.e., the locus to be protected, a correspondingly combative or toxic amount, i.e., insecticidally, acaricidally, fungicidally, bactericidially or microbicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring,

'fumigating,

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 CH W N-ILQ H 5 27.7 g (0.25 mole) of 2-isopropylimidazole and 100 g of sodium carbonate are stirred into a mixture of 1.5 kg

of ice and 1.5 liters of water. While this is being done, 60

pyl-4-phenylhydrazonoimidazolenine of the melting point 168C are obtained.

EXAMPLE 2 3 i CH rr Nah-G (2) I CH3 COGH3 10 23.6 g (0.1 mole) of sodium 2-isopropyl-4-phenylhydrazonoimidazolenine, which is prepared from 0.1 mole of 2-isopropyl 4-phenylhydrazonoimidazolenine by addition thereto of 0.1 mole of sodium ethylate, is

dissolved in 200 ml of anhydrous acetonitrile. 8.6 g

(0.1 1 mole) of acetyl chloride are added dropwise at a temperature of 5C, with stirring, and further stirring is effected for 1 hour at 40C. Thereafter, the solvent is distilled off in a vacuum, the residue is boiled out twice with, in each case, 1 liter of ligroin. 17 g (66 percent of theory) of 2-ispropyl-4-(N-B-phenyl-B-acetybhydrazonoimidazolenine are obtained as yellow crystals of the melting point 129C.

23.6 g (0.1 mole) of sodium 2-isopropyl-4-phenylhydrazonoimidazolenine are dissolved in 250 ml of anhydrous acetonitrile. At a temperature of 0C, 14.1 g (0.15 mole) of chloroformic acid methyl ester are added dropwise and stirring for 17 hours is effected at room temperature. After the solvent has been distilled off in a vacuum, the residue is digested with methylene chloride, filtration from undissolved sodium chloride being effected. 2-isopr0pyl-4-(N-B-phenyl-fi-methyb 'carbonyldioxy)-hydrazonoimidazolenine is obtained as orange-red needles which, again recrystallized from ligroin, have a weight of 18.5 g (68 percent of theory) and a melting point of l 16C.

EXAMPLE 4 23.6 g (0.1 mole) of sodium 2-isopropyl-4-phenylhyhydrazonoimidazolenine of the melting point 137C are obtained.

The compounds specified in the following Table are prepared by methods analogous to those given in the foregoing Examples:

Other compounds in accordance with the present invention include:

2-isopropyl-4-(p-methylthiophenylhydrazono)- imidazolenine,

2-ethyl-4-( p-methylthiophenylhydrazono imidazolenine,

2-ethyl-4-(p-dimethylaminophenylhydrazono)- imidazolenine, and the like.

The activities of the compounds synthesized hereinabove are shown in the following biological tests.

EXAMPLE Agar plate test Test for fungitoxic effectiveness and breadth of the activity spectrum.

Solvent: Acetone Parts by weight: a) 1000 b) 100 To produce a suitable preparation of the active compound, 1 part by weight of the active compound is taken up in the stated amount of solvent.

To potato dextrose agar which has been liquefied by heating there is added the preparation of the active compound in such an amount that the desired concentration of active compound is set up therein. After thorough shaking to achieve a uniform dispersion of the active compound, the agar is poured into Petri dishes under sterile conditions. When the mixture of substrate and active compound has solidified, test fungi from pure cultures are inoculated on to it in small discs of 5 mm diameter. The Petri dishes remain at C for 3 days for incubation.

After this time, the inhibiting action of the active compound on the mycelium growth is determined in l 5 categories, taking into account the untreated control. 0

achieved can be seen from the following Table:

Table 2 Agar plate test I) Active compound Concentration 01. :5! 5 a active compound P H f;

in the substrate 5 .2; .9. S i inwPer 11w as a: as .212 jfl H F rt r1 0 c 0 ago -4 c o imp t-i Ha H ,r: :2 0 t: O O O U Uri 2 2'5 S: I. 1 o h L0 111 5-4 0. o :1. 0

untreated a- 9 P a) 10 Z1! (known) O "H N KCS \l 2 I I 7 100 O O O 10 b) 100 m I f f 5 a 12 i b) 100 o o o 0 14 100 o o o o I 18 a; 10 0 b 100 O O O O O O l 10 O 0 O O r O i 5 b) 1C0 O Q 2 a l O bi 10% o o 1 t Table 2 (oontinued) Agar plate test esppeoemme (which has been cooled to 42C) and is then poured EXAMPLE 6 Mycelium growth test into Petri dishes of 9 cm diameter. Control dishes to which the preparation has not been added are also set up.

Nutrient medium used:

20 parts by weight agar-agar 200 parts by weight potato decoction When the nutrient medium has cooled and solidified, the dishes are inoculated with the species of organisms stated in the Table and incubated at about 21C.

5 parts by weight malt 15 parts by weight dextrose Evaluation is carried out after 4-10 days, dependent upon the speed of growth of the organisms. When eval- 5 parts by weight peptone 2 parts by weight disodium phosphate 0.30 part by weight calcium nitrate uation is carried out, the radial growth of the mycelium on the treated nutrient media is compared with the growth on the control nutrient medium. In the evalua- Proportion of solvent mixture to nutrient medium:

2 parts by weight solvent mixture I00 parts by weight agar nutrient medium. Composition of solvent mixture:

tion of the organism growth, the following characteristic values are used:

0.19 part by weight dimethyl formamide 40 0 no organism growth 0.01 part by weight alkylarylpolyglycol ether 1 very strong inhibition of growth 1.80 parts by weight water 2 medium inhibition of growth The amount of active compound required for the 3 slight inhibition of growth desired concentration of active compound in the nutri- 4 growth equal to that of untreated control. ent medium is mixed with the stated amount of solvent 5 The active compounds, the concentrations of the mixture. The concentrate is thoroughly mixed, in the active compounds and the results can be seen from the stated proportion, with the liquid nutrient medium following Table:

I-iycelium growth test 10 ppm AcLive Compound F ngi and bacterium Active compound A A 4 l 3 4 o A a m n z S s s S a J 2 2 "A "n nw c 2 ms Water:

Table 2 (continued) i-iycelium growth test ppm \ctive Compound Fungi and bacterium Active comp as s; H :1 m a v 55 '5' S '3 H H in H H t4 0 o 1 G H F3 3 1 O H Q 65 S P I at, as a .2 on P451 -ri.V. no at? r: a as at; a: as

26 Q g '6' 1 2 o 2 o o 2 o 1 o 3 3 o o 3 0 1 y o 3 "50 d "0" '5 2"" 6 31 o o 1 o o o 3 39 o o .1 o 1 0 3 49 o o g 2 o EXAMPLE 7 batch of the plants is then inoculated with an aqueous Piricularia and Pellicularia Test Solvent: l.9 parts by weight dlmethyl formamide 0.1 part by weight alkylarylpolyglycol ether 98 parts by weight Dispersing agent:

The amount of active compound required for the desired concentration of active compound in the spray liquor is mixed with the stated amount of solvent, and

suspension of 100,000 to 200,000 spores/ml of Piricularia oryzae and placed in a chamber at 24 26C and 100 percent relative atmospheric humidity. The other batch of the plants is infected with a culture of Pellicularia sasakii grown on malt agar and placed at 28 30C and 100 percent relative atmospheric humidity.

5 to 8 days after inoculation, the infection of all the leaves present at the time of inoculation with Piricularia oryzae is determined as a percentage of the unthe plants infected with Pellicularia sasakii,the infection on the leaf sheaths after the same time is also the conc ntrate is dil t d ith th tat d amount f 0 determined in proportion to the untreated but infected Table 4 control. 0 percent means no infection; 100 percent means that the infection is exactly as great in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table:

Piricula 1 i a( a) and Pelli cularinw) test Infection as a percentage of the infection of the untreated control with a. concentration of active Active protective pr. compound (in 7% by weight) of compound curative cur.

1\- n 1 3 2 S pr. 25 100 our. 100 CH -IlH-CS-S (known) pr. 25 5o 18 pr. 25 o 25 il'i i sai 31% ljigggggj rggtgh) and Pclliculariflb) test Infection as a peroeifimgc offline infection of the untreated contr fiilfvich a concentration of active EXAMPLE 8 35 Seed dressing test/bunt of wheat (seed-borne mycosis) Active protective p::,... compound (in 96 by weight) 01 compound curative cur.

27 pr. 0 75 28 pr. 0

2 pr. 0 i o cui. 13 75 3s pr- 25 i 25 39 pr. 0 o

cur. 25 I 49 pr. 0 o

cover of a layer of muslin and 2 cm of moderately moist soil, is exposed to optimum germination conditions for the spores for 10 days at 10C in a refrigerator.

The germination of the spores on the wheat grains, each of which is contaminated with about 100,000 spores, is subsequently determined microscopically. The smaller the number of spores which have germinated, the more effective is the active compound.

The active compounds, the concentrations of the active compounds in the dressing, the amounts of dressing used and the percentage spore germination can be seen from the following Table:

Table 5 Seed dressingiest bunt oi wheat Concentration Applied amount Spore of active conof dressing gernina- Active compound pound in the in g/kg seed tion in dressing in 7'3 by weight non-dressed 10 I! 2311 -10 108}n 10 l 5 Ch -RHES (known) 21 22 Table -Qontinued Seed dressing tesb bunt 01 wheat Concentration Applied amount 5100;0- of active comof dressing germina- Active compound pound in the in g/kg seed lawn 'in 7 dressing; in '3 by weight It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A method of combating pests selected from the group consisting of fungi and bacteria which comprises applying to said pests or their habitat a fungicidally or bactericidally effective amount of a compound of the formula m R N N-N-Q in which 3. The method according to claim 1, wherein said compound is 2-isopropyl-4-(N-B-pheny-l-fi-acetyD- hydrazonoimidazolenine of the formula 4. The method according to claim 1, wherein said compound is 2-propyl-4-phenylhydrazonoimidazolenine of the formula 5. The method according to claim 1, wherein said compound is 2-isopropyl-4-(p-tolyl)- hydrazonoimidazolenine of the formula 6. The method according to claim 1, wherein said compound is 2-isopropyl-4-[N-B-(4-ethoxyphenyD-B- acetyl]-hydrazonoimidazolenine of the formula CH COCH 3 ,925 ,55 1 24 7. The method according to claim 1, wherein said hydrazonoimidazolenine of the formula compound is 2-methyl-4-(2'-chloro-6'-methyl-phenyl)- hydrazonoimidazolenine of the formula CH IEri C 5 LNNH CH3/K\N N NH CH cu 3 l0 9 Th h d d' l l t 8. The method according to claim 1, wherein said is a gg o accor mg toe alm Wherem Sald pest compound is 2-methyl-4-(2',6'-dimethyl-phenyl)- 

1. A METHOD OF COMBATTING PESTS SELECTED FROM THE GROUP CONSISTING OF FUNGI AND BACTERIA WHICH COMPRISES APPLYING TO SAID PESTS OR THEIR HABITAT A FUNGICIDALLY OR BACTERICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method according to claim 1, wherein said compound is 2-isopropyl-4-phenylhydrazonoimidazolenine of the formula
 3. The method according to claim 1, wherein said compound is 2-isopropyl-4-(N- Beta -phenyl- Beta -acetyl)-hydrazonoimidazolenine of the formula
 4. The method according to claim 1, wherein said compound is 2-propyl-4-phenylhydrazonoimidazolenine of the formula
 5. The method according to claim 1, wherein said compound is 2-isopropyl-4-(p-tolyl)-hydrazonoimidazolenine of the formula
 6. The method according to claim 1, wherein siad compound is 2-isopropyl-4-(N- Beta -(4-ethoxyphenyl)- Beta -acetyl)-hydrazonoimidazolenine of the formula
 7. The method according to claim 1, wherein said compound is 2-methyl-4-(2''-chloro-6''-methyl-phenyl)-hydrazonoimidazolenine of the formula
 8. The method according to claim 1, wherein said compound is 2-methyl-4-(2'',6''-dimethyl-phenyl)-hydrazonoimidazolenine of the formula
 9. The method according to claim 1 wherein said pest is a fungus. 